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US6096830A - Thermoplastic elastomer composition, process for producing the same and golf ball using the same for cover - Google Patents

Thermoplastic elastomer composition, process for producing the same and golf ball using the same for cover Download PDF

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Publication number
US6096830A
US6096830A US08/667,728 US66772896A US6096830A US 6096830 A US6096830 A US 6096830A US 66772896 A US66772896 A US 66772896A US 6096830 A US6096830 A US 6096830A
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Prior art keywords
diene rubber
crosslinking
elastomer composition
thermoplastic resin
thermoplastic elastomer
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US08/667,728
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Kouhei Takemura
Akihiro Nakahara
Yoshinori Sano
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Dunlop Sports Co Ltd
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Sumitomo Rubber Industries Ltd
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Priority claimed from JP27581394A external-priority patent/JP3325408B2/en
Priority claimed from JP27581494A external-priority patent/JP3424864B2/en
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Priority to US08/667,728 priority Critical patent/US6096830A/en
Assigned to SUMITOMO RUBBER INDUSTRIES, LTD. reassignment SUMITOMO RUBBER INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAKAHARA, AKIHIRO, SANO, YOSHINORI, TAKEMURA, KOUHEI
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/006—Physical properties
    • A63B37/0061—Coefficient of restitution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876—Salts thereof, i.e. ionomers

Definitions

  • the present invention relates to a thermoplastic elastomer composition wherein fine crosslinked diene rubber particles are dispersed in a thermoplastic resin, and a process for producing the same.
  • the present invention is also related to a golf ball using the thermoplastic elastomer composition as cover.
  • dynamic crosslinking is meant that rubber is crosslinked while being mixed with molten thermoplastic resin.
  • the dynamic crosslinking has hitherto been carried out to disperse rubber in thermoplastic resin, as described in Japanese Laid-Open Patent Publication No. 5-29653.
  • the dynamic crosslinking is generally conducted in order to improve a processability or a modulus of rubber, and there is very few examples wherein a restoring force (e.g. permanent compression set, elongation set, etc.) of thermoplastic resin are improved.
  • modulus or processability is improved but the restoring force is not improved sufficiently by the conventional dynamic crosslinking.
  • One object of the present invention is to make the restoring force similar to that of the crosslinked rubber without damaging physical properties of the thermoplastic resin, thereby providing a thermoplastic elastomer composition having characteristics of both thermoplastic resin and rubber.
  • Another object of the present invention is to provide a golf ball using the above thermoplastic elastomer for the cover.
  • FIG. 1 is a schematic cross section illustrating one embodiment of the golf ball of the present invention.
  • the above object has been accomplished by dispersing a diene rubber in a thermoplastic resin and dynamically crosslinking the diene rubber with a crosslinking agent to disperse crosslinked diene rubber particles having an average particle size of not more than 10 ⁇ m in the thermoplastic resin, thereby affording a thermoplastic elastomer composition.
  • thermoplastic elastomer composition is considerably improved by dispersing crosslinked diene rubber particles having an average particle size of not more than 10 ⁇ m in the thermoplastic resin by dynamic crosslinking and, at the same time, a decrease in mechanical strength is inhibited, thereby providing a thermoplastic elastomer composition having excellent characteristics of both thermoplastic resin and diene rubber.
  • thermoplastic elastomer composition having excellent characteristics of the thermoplastic resin and diene rubber at, an optimum state when using an ethylene-acrylic acid copolymer neutralized with a metal ion; an ethylene-methacrylic acid copolymer neutralized with a metal ion or an ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion, which is referred to as an ionomer resin, as the thermoplastic resin and using an ethylene-propylene-diene rubber (EPDM) as the diene rubber.
  • EPDM ethylene-propylene-diene rubber
  • U.S. Pat. No. 5,407,998 to Horiuchi et al. discloses a golf ball comprising a core and a cover wherein the cover is mainly made of a mixture composed of an ionomer resin and a diene type rubber at a weight ratio of 95:5-60:40 and the diene type rubber is crosslinked by a crosslinking agent.
  • This patent does not suggest that rubber particles in the ionomer resin are not specified.
  • the dynamic crosslinking should be conducted and terminated as specified in the present invention.
  • the thermoplastic resin to be used for preparing the thermoplastic elastomer composition is not specifically limited, and preferred examples thereof include ethylene-acrylic acid copolymer neutralized with a metal ion, ethylene-methacrylic acid copolymer neutralized with a metal ion, ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion, etc. Among them, the ethylene-methacrylic acid copolymer neutralized with a metal ion is particularly preferred.
  • examples of the alkaline metal ion to neutralize the above copolymers include alkaline metal ions such as sodium ion, potassium ion, lithium ion, etc.; divalent metal ions such as zinc ion, calcium ion, magnesium ion, copper ion, manganese ion, etc.; trivalent metal ions such as aluminum ion, neodymium ion, etc.
  • zinc ion is preferred because binding power of a metal ion aggregate is high and, therefore, a decrease in mechanical strength due to dispersion of crosslinked diene rubber particles is small.
  • ethylene-acrylic acid copolymer neutralized with a metal ion are ethylene-acrylic acid copolymer ionomer resin neutralized with zinc ion [e.g. IOTEK 7010 (trade name), manufactured by Exxon Chemical Co., etc.], ethylene-acrylic acid copolymer ionomer resin neutralized with sodium ion [e.g. IOTEK 8000 (trade name), etc., manufactured by Exxon Chemical Co.] and the like.
  • Preferred examples of the ethylene-methacrylic acid copolymer neutralized with a metal ion are ethylene-methacrylic acid copolymer ionomer resin neutralized with zinc ion [e.g.
  • ethylene-methacrylic acid copolymer ionomer resin neutralized with sodium ion e.g. Hi-milan 1605, Hi-milan 1707 (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.
  • Preferred examples of the ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion are ethylene-acrylic acid-methacrylic acid copolymer ionomer resin neutralized with zinc ion [e.g.
  • Hi-milan (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.] ethylene-acrylic acid-methacrylic acid copolymer ionomer resin neutralized with sodium ion [e.g. Hi-milan (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.] and the like.
  • the diene rubber is not specifically limited, and examples thereof are ethylene-propylene-diene rubber (EPDM), butadiene rubber (BR), butyl rubber (IR), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), etc. Among them, ethylene-propylene-diene rubber and butadiene rubber are particularly preferred.
  • EPDM ethylene-propylene-diene rubber
  • BR butadiene rubber
  • IR butyl rubber
  • SBR styrene-butadiene rubber
  • NBR nitrile-butadiene rubber
  • a weight ratio of the thermoplastic resin to the diene rubber is preferably 30:70 to 95:5, particularly 30:70 to 80:20.
  • the ratio of the thermoplastic resin is less than the above range, the strength of the thermoplastic resin is lowered and it is difficult to obtain a thermoplastic elastomer composition having a high strength.
  • the ratio of the thermoplastic resin is more than the above range, the restoring force such as elongation set of the thermoplastic elastomer composition due to the diene rubber may not be improved.
  • the crosslinking agent is not specifically limited and various crosslinking agents other than peroxides can be used.
  • sulfur a vulcanization accelerator; an oxime; a combination of sulfur and vulcanization accelerator and the like.
  • the vulcanization accelerators are dibenzothiazyl sulfide, N,N'-dicyclohexyl-2-benzothiazyl sulfenamide, hexamethylenetetramine, mercaptobenzothiazole, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, etc.
  • oxime crosslinking agents are p-quinonedioxime, p,p'-dibenzoylquinone dioxime, etc.
  • peroxides are not used as the crosslinking agent because the thermoplastic resin is crosslinked, simultaneously, and it is impossible to carry out molding processing in case of peroxides.
  • An amount of the crosslinking agent is preferably 0.2 to 10 parts by weight, particularly 1 to 5 parts by weight, based on 100 parts by weight of the diene rubber in a mixture of the thermoplastic resin and diene rubber.
  • the amount of the crosslinking agent is less than the above range, the diene rubber is not sufficiently crosslinked and, therefore, the restoring force is not sufficiently improved.
  • the amount of the crosslinking agent is more than the above range, the crosslinking proceeds too rapidly and, therefore, it is difficult to form fine crosslinked rubber particles. Thereby, it is likely to cause poor strength.
  • fillers, processing aids, plasticizers, etc. may be formulated in the composition containing the above thermoplastic resin, diene rubber and crosslinking agent.
  • a temperature of the above formulation materials containing the crosslinking agent i.e. a temperature at the time of dynamic crosslinking
  • a temperature at the time of dynamic crosslinking is suitably within a range between a temperature which is 20° C. lower than an activation reaction temperature of the crosslinking agent and 250° C.
  • the temperature at the time of dynamic crosslinking is suitably 130 to 250° C. because the activation temperature is generally about 150° C.
  • the temperature at the time of dynamic crosslinking is suitably 160 to 250° C. because the activation temperature is generally about 180° C.
  • kneading methods there can be used various kneading methods using a kneader, a Banbury mixer, an extruder, a roll, etc. It is particularly preferred to use a kneader or an extruder because a large shear force is applied thereto.
  • the fillers may be formulated at the time of dynamic crosslinking or may be previously formulated in the diene rubber.
  • the thermoplastic resin may be previously mixed with the diene rubber using roll, kneader, Banbury, extruder, etc., followed by conduct of the dynamic crosslinking, if possible.
  • all formulation materials such as thermoplastic resin, diene rubber, filler, crosslinking agent, etc., may be mixed at a temperature lower than the activation temperature of the crosslinking agent, followed by conducting the dynamic crosslinking.
  • the dynamic crosslinking is controlled with monitoring a torque applied to a mixing machine.
  • the dynamic crosslinking is terminated immediately before or after the torque becomes stable although it has once increased due to the crosslinking of the diene rubber.
  • the torque before dynamic crosslinking is calculated into 100 and the following ratio of the thermoplastic resin to diene rubber is A: ##EQU1## the dynamic crosslinking is terminated upon reaching the torque value of B defined by the equation:
  • the torque is generally displayed in a machine which is used for dynamic crosslinking, but is sometimes expressed as electric current flowing through the machine. Even if the torque is expressed as electric current, the above ideal torque is applicable.
  • the average particle size of the crosslinked diene rubber particles dispersed in the thermoplastic resin is not more than 10 ⁇ m, preferably 0.02 to 8 ⁇ m.
  • the average particle size of crosslinked diene rubber particles dispersed is larger than 10 ⁇ m, the restoring force such as elongation set is not sufficiently improved and the mechanical strength of the thermoplastic resin is lowered.
  • the time varies depending on the kind of the crosslinking agent, formulation, amount of the formulation materials, etc., but is generally about 1 to 60 minutes. For example, when using sulfur in combination with the vulcanization accelerator, it is about 2 to 30 minutes. When using the oxime crosslinking agent, it is about 3 to 60 minutes.
  • thermoplastic elastomer of the present invention can be applied for various utilities.
  • thermoplastic elastomer composition of the present invention is used as a base polymer of a cover of a golf ball, its physical performance is fully advantageous.
  • cover of the golf ball it can be covered on either a core for solid golf balls (solid core) or a core for thread wound golf balls (thread wound core).
  • the solid core may be either a single-layer structure core or a multi-layer core of two or more layers.
  • the core for a two-piece golf ball those obtained by subjecting a rubber composition to a press vulcanization (crosslinking) to compress with heating (e.g. at a temperature of 140 to 170° C. for 10 to 40 minutes) into a spherical vulcanized material can be used.
  • the rubber composition is composed of 100 parts by weight of a butadiene rubber, 10 to 60 parts by weight of at least one vulcanizing agent (crosslinking agent) of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids (e.g.
  • acrylic acid, methacrylic acid, etc.) or metal salts thereof and functional monomers e.g. trimethylolpropane trimethacrylate, etc.
  • a filler e.g. zinc oxide, barium sulfate, etc.
  • a peroxide e.g. dicumyl peroxide, etc.
  • the thread wound core is composed of a center and a thread rubber wound on the center.
  • a center either a liquid center or a rubber center can be used.
  • the rubber center there can be used those obtained by vulcanizing the same rubber composition as that of the solid core.
  • the thread rubber may be those which have hitherto been used.
  • it can be obtained by vulcanizing a rubber composition which is a mixture of an antioxidant, a vulcanizing accelerator and sulfur formulated with a natural rubber or a natural rubber and synthetic polyisoprene.
  • the core is not limited to the solid core and thread wound core.
  • a method of covering the cover on the core is not specifically limited, but may be a general method.
  • a method comprising molding a composition for the cover prepared by formulating a suitable amount of a requisite additive in the specific base material for the cover into a semi-spherical half-shell in advance, covering a core the with two half-shells and then subjecting the resultant core plus sphere to a pressure molding at 100 to 170° C. for 1 to 15 minutes, or a second method may be used comprising subjecting the composition for the cover to an injection molding directly to cover the core.
  • the thickness of the cover is generally about 1 to 4 mm.
  • dimples may be formed on the surface of the ball. If necessary, paint or marking may be provided after cover molding.
  • the golf ball shown in FIG. 1 is a two-piece solid golf ball comprising a core 1 of a vulcanized molded article of a rubber composition and a cover 2 for covering the core.
  • the core 1 is a solid core, but is not specifically limited.
  • the above vulcanized molded material of the rubber composition comprising a butadiene rubber as the main material is preferably used as the solid core.
  • the cover 2 is made of a cover composition, comprising the above specific thermoplastic elastomer as a base polymer.
  • 2a is a dimple provided on the cover 2.
  • the core 1 is composed of the vulcanized molded article of the rubber composition of a single-layer structure, but it may be a solid core of a two-layer structure which is obtained by forming an outer core of a vulcanized molded material of a rubber composition comprising a butadiene rubber as a main material around an inner core of a vulcanized molded material of a rubber composition comprising a butadiene rubber as a main material, or a thread wound core which is obtained by forming a thread rubber at a stretched state around a liquid or rubber center.
  • a suitable number of dimples 2a may be provided on the cover 2 so that desired flight characteristics may be obtained.
  • paint finishing and marking may be optionally provided on the surface of the golf ball.
  • the present invention provides a thermoplastic elastomer composition which has characteristics of both thermoplastic resins and diene rubber.
  • the composition has excellent restoring force and excellent characteristics (e.g. tensile strength, elongation, etc.).
  • the present invention provides a golf ball which has excellent shot feel and high resilience performances and attains a long flight distance.
  • thermoplastic resin diene rubber and crosslinking agent were used in the amount described in Table 1 while changing the ratio of the diene rubber to the thermoplastic resin, and the mixture was subjected to dynamic crosslinking.
  • the components were used in the amount described in Table 2, and the mixture was only kneaded and were not subjected to dynamic crosslinking.
  • Hi-milan AM7315 (trade name, ethylene-methacrylic acid copolymer ionomer resin neutralized with a zinc ion manufactured by Mitsui Du Pont Polychemical Co., Ltd.)
  • Esprene 501A (trade name, ethylene-propylene-diene rubber (EPDM) manufactured by Sumitomo Chemical Industries Co., Ltd.)
  • Balnoc (trade name, p,p'-dibenzoylquinone dioxime manufactured by Nihon Yushi Co., Ltd.)
  • the dynamic crosslinking in Examples 1 to 3 was carried out with kneading the formulation materials shown in Table 1 at 180° C. at 100 rpm using a laboplast mill manufactured by Toyo Seiki Co., Ltd. Then, the sample obtained after the termination of the dynamic crosslinking was pulverized into pieces of 3 to 5 mm, which was subjected to sheet press at 170° C. for 15 minutes to give a sample for the measurement of physical properties.
  • the termination of the dynamic crosslinking in Examples 1 to 3 was carried out by a method comprising terminating immediately after satisfying the above ideal torque ratio and reaching the maximum torque ratio.
  • the kneading in Comparative Examples 1 to 3 was carried out by a method comprising kneading for the same time as that required for the dynamic crosslinking in the corresponding Example.
  • the particle size was determined by taking a reflection electron image micrograph using a scanning electron microscope (Model T-220A, manufactured by JEOL Co.) and measuring a perpendicular length of any fifty rubber particles. The numerical value due to number average was taken as an average particle size.
  • no dynamic crosslinking was carried out in Comparative Examples 1 to 3 and the thermoplastic resin and diene rubber form a continuous layer, respectively. Therefore, the particle size could not be measured.
  • physical properties (tensile strength, elongation and elongation set) of the resulting crosslinked material were measured according to JIS-K6301 (Physical test method of vulcanized rubber).
  • the amounts of the respective formulation materials in the respective tables are parts by weight.
  • the thermoplastic resin and diene rubber are indicated by the trade name in the tables.
  • thermoplastic elastomer compositions of Examples 1 to 3 showed a small elongation set and were superior in restoring force. That is, the physical properties vary depending on the ratio of the thermoplastic resin to the diene rubber, but the thermoplastic elastomer composition of Example 1 wherein the ratio of the thermoplastic resin is the highest showed an elongation set of 22.3%. It showed a small elongation set and was superior in restoring force to that of Comparative Example 1 wherein the formulation is the same but no crosslinking agent is contained as well as that of Comparative Example 3 wherein the ratio of the thermoplastic resin is the smallest
  • Example 2 According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization as the crosslinking agent, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, and physical properties thereof were measured.
  • Example 3 The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked material of Example 4 are shown in Table 3.
  • Comparative Example which corresponds to Example 4 is Comparative Example 1 and, therefore, the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked material of Comparative Example 1 are also shown in Table 3.
  • the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
  • crosslinking agent used in Example 4 is as follows.
  • Vulcanization accelerator tetrabutylthiuram disulfide, Nocceler TBT-N (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.
  • thermoplastic elastomer composition of Example 4 showed a small elongation set and was superior in restoring force to that of the corresponding Comparative Example 1. In addition, a considerable decrease in tensile strength and elongation was not observed.
  • thermoplastic elastomer composition in Examples 5 to 6.
  • thermoplastic elastomer composition in Comparative Examples 4 to 5. Then, their physical properties were compared.
  • the formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 5 to 6 are shown in Table 4.
  • the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked materials of Comparative Examples 4 to 5 are shown in Table 5.
  • the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
  • diene rubbers used in Examples 5 to 6 and Comparative Examples 4 to 5 are as follows.
  • Esprene 301 ethylene-propylene-diene rubber (EPDM), manufactured by Sumitomo Chemical Industries Co., Ltd.)
  • Nodel 1470 ethylene-propylene-diene rubber (EPDM), manufactured by Showa Denko Co., Ltd.)
  • thermoplastic elastomer compositions of Examples 5 to 6 showed a small elongation set and were superior in restoring force to those of Comparative Examples 4 to 5. In addition, a considerable decrease in tensile strength and elongation was not observed.
  • thermoplastic elastomer composition According to the same manner as that described in Example 1 except for using a butadiene rubber as the diene rubber and changing the amount thereof, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Examples 7 to 8. According to the same manner as that described in Example 1 except for using a butadiene rubber as the diene rubber and changing the amount thereof, the mixture was only kneaded to produce a thermoplastic elastomer composition, in Comparative Examples 6 to 7. Then, their physical properties were compared.
  • the formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 7 to 8 are shown in Table 6.
  • the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked materials of Comparative Examples 6 to 7 are shown in Table 7.
  • the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
  • diene rubber used in Examples 7 to 8 and Comparative Examples 6 to 7 is as follows.
  • thermoplastic elastomer compositions of Examples 7 to 8 showed a small elongation set and were superior in restoring force to those of Comparative Examples 6 to 7. In addition, a considerable decrease in tensile strength and elongation was not observed, and they were rather superior.
  • Example 2 According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization accelerator, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition. Then, their physical properties were measured.
  • crosslinking agent used in Examples 9 to 10 is as follows.
  • Vulcanization accelerator tetrabutylthiuram disulfide, Nocceler TT (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.
  • Comparative Examples corresponding to Examples 9 to 10 are Comparative Examples 6 to 7. As is apparent from the results shown in Tables 8 and 7, the thermoplastic elastomer compositions of Examples 9 to 10 showed a small elongation set and were superior in restoring force to those of Comparative Examples 6 to 7. In addition, a considerable decrease in tensile strength and elongation was not observed.
  • Example 11 According to the same manner as that described in Example 1 except for changing the revolution number at the time of dynamic crosslinking (changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Example 11. According to the same manner as that described in Comparative Example 1 except for changing the revolution number at the time of kneading (changing from 100 rpm to 150 rpm), the mixture was kneaded to produce a thermoplastic elastomer composition, in Comparative Example 8. In Example 11, a change in average particle size of crosslinked diene rubber particles and that in physical properties were examined. In Comparative Example 8, a change in physical properties was examined.
  • thermoplastic elastomer composition of Example 11 showed a small elongation set and was superior in restoring force to that of Comparative Example 8. In addition, a considerable decrease in tensile strength and elongation was not admitted observed, and they were rather superior.
  • thermoplastic elastomer composition of Example 11 was compared with that of Example 11. As a result, the average particle size of crosslinked diene rubber particles became small from 8 ⁇ m to 3 ⁇ m and, at the same time, the elongation set became small from 22.3% to 13.7%. On the other hand, in Comparative Examples 8 and 1, the elongation set became small but the tensile strength and elongation were lowered.
  • Example 4 According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization accelerator according to the same manner as that described in Example 4 except for changing the revolution number at the time of dynamic crosslinking (i.e. changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition. Then, a change in average particle size of crosslinked diene rubber particles and that in physical properties were examined.
  • Example 12 The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio of Example 12 are shown in Table 10. Since Comparative Example corresponding to Example 12 is Comparative Example 8, the average particle size of crosslinked diene rubber particles and physical properties of the crosslinked material as well as formulation, revolution number at the time of kneading, time and physical properties of Comparative Example 8 are shown in Table 10. In addition, the indicating method and measuring method of the particle size and physical properties are the same as those of Example 1.
  • crosslinking agent used in Example 12 is as follows.
  • Vulcanization accelerator tetrabutylthiuram disulfide, Nocceler TBT-N (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.
  • thermoplastic elastomer composition of Example 12 showed a small elongation set and was superior in restoring force to that of Comparative Example 8. In addition, a considerable decrease in tensile strength and elongation was not observed, and they were rather superior.
  • thermoplastic elastomer composition of Example 12 was compared with that of Example 4. As a result, the average particle size of crosslinked diene rubber particles became small from 1.2 ⁇ m to 0.7 ⁇ m and, at the same time, the elongation set became small from 23.1% to 16.7%.
  • thermoplastic elastomer composition in Examples 13 to 15.
  • thermoplastic elastomer composition in Comparative Examples 9 to 10.
  • physical properties of the thermoplastic resin Hi-milan AM7315 (trade name, ionomer resin) alone are shown in Comparative Example 11.
  • the formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 13 to 15 are shown in Table 11.
  • the formulation amount, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Comparative Examples 9 to 10 are shown in Table 11.
  • the indicating method and measuring method of the particle size and physical properties are the same as those of Example 1.
  • thermoplastic elastomer compositions of Examples 13 to 15 showed a small elongation set and were superior in restoring force to those of Comparative Examples 9 to 10. In addition, they had the same or better characteristics (e.g. tensile strength, elongation, etc.) as that of Comparative Example 11 using the thermoplastic resin alone.
  • BR01 trade name, butadiene rubber manufactured by Nihon Synthetic Rubber Co., Ltd.
  • Examples 16 to 18 the following ionomer resin, diene rubber and crosslinking agent were used in the amount described in Table 13 while changing a ratio of the diene rubber to the ionomer resin, and the mixture was subjected to dynamic crosslinking. In Comparative Examples 12 to 14, they were used in the amount described in Table 14, and the mixture was only kneaded.
  • Hi-milan AM7315 (trade name, ethylene-methacrylic acid copolymer ionomer resin neutralized with a zinc ion manufactured by Mitsui Du Pont Polychemical Co., Ltd.)
  • Esprene 501 (trade name, ethylene-propylene-diene rubber (EPDM) manufactured by Sumitomo Chemical Industries Co., Ltd.)
  • Balnoc DGM (trade name, p,p'-dibenzoylquinone dioxime manufactured by Nihon Yushi Co., Ltd.)
  • the termination of the dynamic crosslinking in Examples 16 to 18 was carried out by a method comprising terminating immediately after satisfying the above ideal torque ratio and reaching the maximum torque ratio.
  • the kneading in Comparative Examples 12 to 14 was carried out by a method comprising kneading for the same time as that required for the dynamic crosslinking in the corresponding Example.
  • the amounts of the respective formulation materials in the respective tables are parts by weight.
  • the thermoplastic resin and diene rubber are indicated by the trade name in the tables.
  • a two-piece solid golf ball having an outer diameter of 42.7 mm was made by pulverizing the cover composition of the above (2) into pieces of 3 to 5 mm, molding them to form a half-shell, covering the core of the above (1) using two half-shells, followed by heat molding at 160° C. for 3 minutes.
  • the weight, resilience coefficient and flight distance of the resulting golf ball were measured and the shot feel was determined.
  • the measuring method of the resilience coefficient and flight distance as well as evaluation method of the shot feel were as follows.
  • a stainless steel column (198 g) is launched at an initial velocity of 35 m/second using an air gun to strike it against a golf ball ahead of the column. Then, the velocity of the column and golf ball before and after striking is measured, respectively, using two photoelectric tubes to calculate a resilience coefficient from each velocity and weight. The above measurement is carried out as to eight golf balls and the average value is taken as the value of the resilience coefficient.
  • a golf ball is practically hit with a No. 1 wood club by 5 top professional golfers and shot feel is evaluated according to the following seven-grade criteria.
  • a sample for measurement was made by pulverizing the cover composition of the above (2) into pieces of 3 to 5 mm and subjecting to heat molding under pressure at 160° C. for 3 minutes to form a sheet.
  • the particle size was determined by taking a reflection electron image micrograph using a scanning electron microscope (Model T-220A, manufactured by JEOL Co.) and measuring a perpendicular length of any fifty rubber particles. The numerical value due to number average was taken as an average particle size.
  • no dynamic crosslinking was carried out in Comparative Examples 12 to 14 and the thermoplastic resin and diene rubber form a continuous layer, respectively. Therefore, the particle size could not be measured.
  • the formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as weight, resilience coefficient, flight distance and evaluation results of the shot feel of the resulting golf balls of Examples 16 to 18 are shown in Table 13.
  • the formulation of the cover composition, revolution number at the time of kneading and time as well as weight, resilience coefficient, flight distance and evaluation results of the shot feel of the resulting golf balls of Comparative Examples 12 to 14 are shown in Table 14.
  • the golf balls of Examples 16 to 18 showed a large resilience coefficient and long flight distance and were also superior in shot feel to those of Comparative Examples 12 to 14 wherein the formulation is the same but no crosslinking agent is contained.
  • Example 16 According to the same manner as that described in Example 16 except for changing the kind of the diene rubber, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 19 to 20. According to the same manner as that described in Example 16 except for changing the kind of the diene rubber, the mixture was only kneaded to prepare a cover composition, in Comparative Examples 15 to 16. Then, their characteristics were evaluated.
  • diene rubbers used in Examples 19 to 20 and Comparative Examples 15 to 16 are as follows.
  • Esprene 301 ethylene-propylene-diene rubber (EPDM), manufactured by Sumitomo Chemical Industries Co., Ltd.)
  • Nodel 1470 ethylene-propylene-diene rubber (EPDM), manufactured by Showa Denko Co., Ltd.)
  • the formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as characteristics of the resulting golf balls of Examples 19 to 20 are shown in Table 15.
  • the formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 15 to 16 are shown in Table 16.
  • the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
  • Example 16 According to the same manner as that described in Example 16 except for using a butadiene rubber as the diene rubber while changing the amount, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 21 to 22. According to the same manner as that described in Example 16 except for using a butadiene rubber as the diene rubber while changing the amount, the mixture was only kneaded to prepare a cover composition, in Comparative Examples 17 to 18. Then, their characteristics were measured.
  • diene rubbers used in Examples 21 to 22 and Comparative Examples 17 to 18 are as follows.
  • BR01 Hi-cis butadiene rubber (EPDM), manufactured by Nihon Synthetic Rubber Co., Ltd.)
  • the formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles of as well as characteristics of the resulting golf balls of Examples 21 to 22 are shown in Table 17.
  • the formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 17 to 18 are shown in Table 18.
  • the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
  • Example 23 According to the same manner as that described in Example 16 except for changing the revolution number at the time of dynamic crosslinking (changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Example 23. According to the same manner as that described in Example 12 except for changing the revolution number at the time of kneading (changing from 100 rpm to 150 rpm), the mixture was only kneaded to prepare a cover composition, in Comparative Example 19. Then, their characteristics were measured.
  • the formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and characteristics of the resulting golf ball of Example 23 as well as formulation of the cover composition, revolution number at the time of kneading, time and characteristics of the resulting golf ball of Comparative Example 19 are shown in Table 19 respectively.
  • the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
  • the golf ball of Example 23 showed a large resilience coefficient and long flight distance and was also superior in shot feel to that of Comparative Example 19.
  • Example 23 was compared with that of Example 16.
  • the average particle size of crosslinked diene rubber particles became small from 6 ⁇ m to 2 ⁇ m and, at the same time, the resilience coefficient and flight distance were improved.
  • the resilience coefficient of the golf ball of Comparative Example 19 is slightly smaller than that of Comparative Example 12, and the shot feel became inferior.
  • Example 16 According to the same manner as that described in Example 16 except for changing the amount of the crosslinking agent, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 24 to 25. According to the same manner as that described in Example 16 except for changing the amount of the crosslinking agent beyond the range of the present invention, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Comparative Examples 20 to 21. In Comparative Example 21, Hi-milan AM7315 (trade name, ionomer resin) alone was used as the cover composition to make a golf ball, and characteristics were evaluated.
  • Comparative Example 21 Hi-milan AM7315 (trade name, ionomer resin) alone was used as the cover composition to make a golf ball, and characteristics were evaluated.
  • the formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as characteristics of the resulting golf balls of Examples 24 to 25 are shown in Table 20.
  • the formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 20 to 21 and ball characteristics of Comparative Example 22 are shown in Table 21.
  • the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
  • the golf balls of Examples 24 to 25 showed a large resilience coefficient and flight distance and were also superior in shot feel to those of Comparative Examples 20 to 22.

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Abstract

Disclosed is a thermoplastic elastomer composition having characteristics of both thermoplastic resin and rubber, and a golf ball using the thermoplastic elastomer composition as the cover. The thermoplastic elastomer composition of the present invention comprises a thermoplastic resin and crosslinked diene rubber particles having an average diameter of not more than 10 μm dispersed in the thermoplastic resin, which is prepared by dynamic crosslinking diene rubber dispersed in the thermoplastic resin with crosslinking agent.

Description

This application is a continuation-in-part of application Ser. No. 08/541,267, filed Oct. 12 1995, now abandoned.
FIELD OF THE INVENTION
The present invention relates to a thermoplastic elastomer composition wherein fine crosslinked diene rubber particles are dispersed in a thermoplastic resin, and a process for producing the same. The present invention is also related to a golf ball using the thermoplastic elastomer composition as cover.
BACKGROUND OF THE INVENTION
By the term "dynamic crosslinking" is meant that rubber is crosslinked while being mixed with molten thermoplastic resin. The dynamic crosslinking has hitherto been carried out to disperse rubber in thermoplastic resin, as described in Japanese Laid-Open Patent Publication No. 5-29653. However, the dynamic crosslinking is generally conducted in order to improve a processability or a modulus of rubber, and there is very few examples wherein a restoring force (e.g. permanent compression set, elongation set, etc.) of thermoplastic resin are improved.
Under these circumstances, it is reported in Japanese Laid-Open Patent Publication Nos. 2-235949 and 4-63850 that a restoring force of a thermoplastic resin is improved. According to the methods disclosed in the prior art, the permanent compression set of the thermoplastic resin is improved to some extent but the degree of improvement is small in comparison with the permanent compression set of the rubber.
As described above, modulus or processability is improved but the restoring force is not improved sufficiently by the conventional dynamic crosslinking.
OBJECTS OF THE INVENTION
One object of the present invention is to make the restoring force similar to that of the crosslinked rubber without damaging physical properties of the thermoplastic resin, thereby providing a thermoplastic elastomer composition having characteristics of both thermoplastic resin and rubber.
Another object of the present invention is to provide a golf ball using the above thermoplastic elastomer for the cover.
These objects as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description with reference to the accompanying drawings.
BRIEF EXPLANATION OF DRAWINGS
FIG. 1 is a schematic cross section illustrating one embodiment of the golf ball of the present invention.
SUMMARY OF THE INVENTION
According to the present invention, the above object has been accomplished by dispersing a diene rubber in a thermoplastic resin and dynamically crosslinking the diene rubber with a crosslinking agent to disperse crosslinked diene rubber particles having an average particle size of not more than 10 μm in the thermoplastic resin, thereby affording a thermoplastic elastomer composition.
That is, the present inventors have intensively studied to disperse the rubber in the thermoplastic resin. As a result, it has been found that a restoring force is considerably improved when the crosslinked diene rubber particles to be dispersed are fine and, at the same time, a decrease in mechanical strength becomes small when a resin matrix forms a continuous layer. According to the resulting knowledge, a restoring force of the thermoplastic elastomer composition is considerably improved by dispersing crosslinked diene rubber particles having an average particle size of not more than 10 μm in the thermoplastic resin by dynamic crosslinking and, at the same time, a decrease in mechanical strength is inhibited, thereby providing a thermoplastic elastomer composition having excellent characteristics of both thermoplastic resin and diene rubber.
Particularly, a restoring force is considerably improved and a thermoplastic elastomer composition having excellent characteristics of the thermoplastic resin and diene rubber at, an optimum state when using an ethylene-acrylic acid copolymer neutralized with a metal ion; an ethylene-methacrylic acid copolymer neutralized with a metal ion or an ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion, which is referred to as an ionomer resin, as the thermoplastic resin and using an ethylene-propylene-diene rubber (EPDM) as the diene rubber. In addition, it is possible to disperse crosslinked diene rubber fine particles in the thermoplastic resin by controlling torque change at the time of dynamic crosslinking.
U.S. Pat. No. 5,407,998 to Horiuchi et al. discloses a golf ball comprising a core and a cover wherein the cover is mainly made of a mixture composed of an ionomer resin and a diene type rubber at a weight ratio of 95:5-60:40 and the diene type rubber is crosslinked by a crosslinking agent. This patent does not suggest that rubber particles in the ionomer resin are not specified. In order to finely disperse the rubber particles having not more than 10 μm in the thermoplastic resin, the dynamic crosslinking should be conducted and terminated as specified in the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be explained in detail.
In the present invention, the thermoplastic resin to be used for preparing the thermoplastic elastomer composition is not specifically limited, and preferred examples thereof include ethylene-acrylic acid copolymer neutralized with a metal ion, ethylene-methacrylic acid copolymer neutralized with a metal ion, ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion, etc. Among them, the ethylene-methacrylic acid copolymer neutralized with a metal ion is particularly preferred. In addition, examples of the alkaline metal ion to neutralize the above copolymers include alkaline metal ions such as sodium ion, potassium ion, lithium ion, etc.; divalent metal ions such as zinc ion, calcium ion, magnesium ion, copper ion, manganese ion, etc.; trivalent metal ions such as aluminum ion, neodymium ion, etc. Among them, zinc ion is preferred because binding power of a metal ion aggregate is high and, therefore, a decrease in mechanical strength due to dispersion of crosslinked diene rubber particles is small.
Preferred examples of the above ethylene-acrylic acid copolymer neutralized with a metal ion are ethylene-acrylic acid copolymer ionomer resin neutralized with zinc ion [e.g. IOTEK 7010 (trade name), manufactured by Exxon Chemical Co., etc.], ethylene-acrylic acid copolymer ionomer resin neutralized with sodium ion [e.g. IOTEK 8000 (trade name), etc., manufactured by Exxon Chemical Co.] and the like. Preferred examples of the ethylene-methacrylic acid copolymer neutralized with a metal ion are ethylene-methacrylic acid copolymer ionomer resin neutralized with zinc ion [e.g. Hi-milan 1705, Hi-milan 1706, Hi-milan AM7315, Hi-milan AM7317 (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.], ethylene-methacrylic acid copolymer ionomer resin neutralized with sodium ion [e.g. Hi-milan 1605, Hi-milan 1707 (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.] and the like. Preferred examples of the ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion are ethylene-acrylic acid-methacrylic acid copolymer ionomer resin neutralized with zinc ion [e.g. Hi-milan (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.], ethylene-acrylic acid-methacrylic acid copolymer ionomer resin neutralized with sodium ion [e.g. Hi-milan (trade name), etc. manufactured by Mitsui Du Pont Polychemical Co., Ltd.] and the like.
On the other hand, the diene rubber is not specifically limited, and examples thereof are ethylene-propylene-diene rubber (EPDM), butadiene rubber (BR), butyl rubber (IR), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), etc. Among them, ethylene-propylene-diene rubber and butadiene rubber are particularly preferred.
A weight ratio of the thermoplastic resin to the diene rubber is preferably 30:70 to 95:5, particularly 30:70 to 80:20. When the ratio of the thermoplastic resin is less than the above range, the strength of the thermoplastic resin is lowered and it is difficult to obtain a thermoplastic elastomer composition having a high strength. On the other hand, when the ratio of the thermoplastic resin is more than the above range, the restoring force such as elongation set of the thermoplastic elastomer composition due to the diene rubber may not be improved.
The crosslinking agent is not specifically limited and various crosslinking agents other than peroxides can be used. Examples thereof are sulfur; a vulcanization accelerator; an oxime; a combination of sulfur and vulcanization accelerator and the like. Examples of the vulcanization accelerators are dibenzothiazyl sulfide, N,N'-dicyclohexyl-2-benzothiazyl sulfenamide, hexamethylenetetramine, mercaptobenzothiazole, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, etc. But it is not specifically limited and there can be used various vulcanization accelerators which are generally used in the rubber formulation. Examples of the oxime crosslinking agents are p-quinonedioxime, p,p'-dibenzoylquinone dioxime, etc. However, peroxides are not used as the crosslinking agent because the thermoplastic resin is crosslinked, simultaneously, and it is impossible to carry out molding processing in case of peroxides.
An amount of the crosslinking agent is preferably 0.2 to 10 parts by weight, particularly 1 to 5 parts by weight, based on 100 parts by weight of the diene rubber in a mixture of the thermoplastic resin and diene rubber. When the amount of the crosslinking agent is less than the above range, the diene rubber is not sufficiently crosslinked and, therefore, the restoring force is not sufficiently improved. On the other hand, when the amount of the crosslinking agent is more than the above range, the crosslinking proceeds too rapidly and, therefore, it is difficult to form fine crosslinked rubber particles. Thereby, it is likely to cause poor strength.
In addition, in order to obtain desired physical properties, fillers, processing aids, plasticizers, etc. may be formulated in the composition containing the above thermoplastic resin, diene rubber and crosslinking agent.
A temperature of the above formulation materials containing the crosslinking agent, i.e. a temperature at the time of dynamic crosslinking, is suitably within a range between a temperature which is 20° C. lower than an activation reaction temperature of the crosslinking agent and 250° C. For example, when using sulfur in combination with the vulcanization accelerator, the temperature at the time of dynamic crosslinking is suitably 130 to 250° C. because the activation temperature is generally about 150° C. In addition, in the case of the oxime crosslinking agent, the temperature at the time of dynamic crosslinking is suitably 160 to 250° C. because the activation temperature is generally about 180° C. When the temperature at the time of dynamic crosslinking is lower than the above range, the crosslinking of the diene rubber does not proceed sufficiently. In addition, even if crosslinking arises the, working efficiency is inferior because of low the crosslinking rate. On the other hand, when the temperature at the time of dynamic crosslinking is higher than the above range, the physical properties of the diene rubber are deteriorated and it is difficult to improve the restoring force such as the elongation set.
As kneading methods, there can be used various kneading methods using a kneader, a Banbury mixer, an extruder, a roll, etc. It is particularly preferred to use a kneader or an extruder because a large shear force is applied thereto.
The fillers may be formulated at the time of dynamic crosslinking or may be previously formulated in the diene rubber. In addition, the thermoplastic resin may be previously mixed with the diene rubber using roll, kneader, Banbury, extruder, etc., followed by conduct of the dynamic crosslinking, if possible. When the mixing can be carried out at a temperature lower than the activation temperature of the crosslinking agent, all formulation materials such as thermoplastic resin, diene rubber, filler, crosslinking agent, etc., may be mixed at a temperature lower than the activation temperature of the crosslinking agent, followed by conducting the dynamic crosslinking.
It is preferred that the dynamic crosslinking is controlled with monitoring a torque applied to a mixing machine. The dynamic crosslinking is terminated immediately before or after the torque becomes stable although it has once increased due to the crosslinking of the diene rubber. For example, asuming that the torque before dynamic crosslinking is calculated into 100 and the following ratio of the thermoplastic resin to diene rubber is A: ##EQU1## the dynamic crosslinking is terminated upon reaching the torque value of B defined by the equation:
B=100+(10×A) or more.
Hereinafter, this torque B is referred to as an ideal torque ratio. It is particularly preferred to satisfy the condition that the torque is more than the above value of the ideal torque ratio and to terminate the dynamic crosslinking after reaching the maximum value. If the actual torque value before dynamic crosslinking is 20 which times 5 to be 100, and A is rubber weight being 30 g/(resin weight being 70 g+rubber weight being 30 g)=3/10, then the ideal torque is 100+(10×3/10)=103 which is then divided by 5 to be 20.6. Accordingly, when the actual torque exceeds 20.6, the dynamic crosslinking is terminated. The torque is generally displayed in a machine which is used for dynamic crosslinking, but is sometimes expressed as electric current flowing through the machine. Even if the torque is expressed as electric current, the above ideal torque is applicable.
In the present invention, the average particle size of the crosslinked diene rubber particles dispersed in the thermoplastic resin is not more than 10 μm, preferably 0.02 to 8 μm. When the average particle size of crosslinked diene rubber particles dispersed is larger than 10 μm, the restoring force such as elongation set is not sufficiently improved and the mechanical strength of the thermoplastic resin is lowered.
It is advantageous for the improvement of the restoring force and prevention of a decrease in mechanical strength to use crosslinked diene rubber particles having a smaller particle size. When the particle size is too small, the restoring force of the thermoplastic elastomer is similar to that of the thermoplastic resin and the restoring force is not improved. Therefore, those having an average particle size of not less than 0.001 μm are preferred for practical use.
It is suitable to control the termination of the dynamic crosslinking by the torque value, as described above. The time varies depending on the kind of the crosslinking agent, formulation, amount of the formulation materials, etc., but is generally about 1 to 60 minutes. For example, when using sulfur in combination with the vulcanization accelerator, it is about 2 to 30 minutes. When using the oxime crosslinking agent, it is about 3 to 60 minutes.
The thermoplastic elastomer of the present invention can be applied for various utilities. When the thermoplastic elastomer composition of the present invention is used as a base polymer of a cover of a golf ball, its physical performance is fully advantageous. When using it as the cover of the golf ball, it can be covered on either a core for solid golf balls (solid core) or a core for thread wound golf balls (thread wound core).
The solid core may be either a single-layer structure core or a multi-layer core of two or more layers. For example, as the core for a two-piece golf ball, those obtained by subjecting a rubber composition to a press vulcanization (crosslinking) to compress with heating (e.g. at a temperature of 140 to 170° C. for 10 to 40 minutes) into a spherical vulcanized material can be used. The rubber composition is composed of 100 parts by weight of a butadiene rubber, 10 to 60 parts by weight of at least one vulcanizing agent (crosslinking agent) of α, β-ethylenically unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid, etc.) or metal salts thereof and functional monomers (e.g. trimethylolpropane trimethacrylate, etc.), 10 to 30 parts by weight of a filler (e.g. zinc oxide, barium sulfate, etc.), 0.5 to 5 parts by weight of a peroxide (e.g. dicumyl peroxide, etc.) and 0.1 to 1 part by weight of an antioxidant.
The thread wound core is composed of a center and a thread rubber wound on the center. As the center, either a liquid center or a rubber center can be used. As the rubber center, there can be used those obtained by vulcanizing the same rubber composition as that of the solid core.
The thread rubber may be those which have hitherto been used. For example, it can be obtained by vulcanizing a rubber composition which is a mixture of an antioxidant, a vulcanizing accelerator and sulfur formulated with a natural rubber or a natural rubber and synthetic polyisoprene. The core is not limited to the solid core and thread wound core.
A method of covering the cover on the core is not specifically limited, but may be a general method. For example, there can be employed a method comprising molding a composition for the cover prepared by formulating a suitable amount of a requisite additive in the specific base material for the cover into a semi-spherical half-shell in advance, covering a core the with two half-shells and then subjecting the resultant core plus sphere to a pressure molding at 100 to 170° C. for 1 to 15 minutes, or a second method may be used comprising subjecting the composition for the cover to an injection molding directly to cover the core. The thickness of the cover is generally about 1 to 4 mm. In the case of cover molding, dimples may be formed on the surface of the ball. If necessary, paint or marking may be provided after cover molding.
Then, the construction of the golf ball of the present invention will be explained with reference to the accompanying drawing.
The golf ball shown in FIG. 1 is a two-piece solid golf ball comprising a core 1 of a vulcanized molded article of a rubber composition and a cover 2 for covering the core.
The core 1 is a solid core, but is not specifically limited. For example, the above vulcanized molded material of the rubber composition comprising a butadiene rubber as the main material is preferably used as the solid core. The cover 2 is made of a cover composition, comprising the above specific thermoplastic elastomer as a base polymer. In addition, 2a is a dimple provided on the cover 2. The core 1 is composed of the vulcanized molded article of the rubber composition of a single-layer structure, but it may be a solid core of a two-layer structure which is obtained by forming an outer core of a vulcanized molded material of a rubber composition comprising a butadiene rubber as a main material around an inner core of a vulcanized molded material of a rubber composition comprising a butadiene rubber as a main material, or a thread wound core which is obtained by forming a thread rubber at a stretched state around a liquid or rubber center.
A suitable number of dimples 2a may be provided on the cover 2 so that desired flight characteristics may be obtained. In addition, paint finishing and marking may be optionally provided on the surface of the golf ball.
As described above, the present invention provides a thermoplastic elastomer composition which has characteristics of both thermoplastic resins and diene rubber. For example, the composition has excellent restoring force and excellent characteristics (e.g. tensile strength, elongation, etc.).
Also, the present invention provides a golf ball which has excellent shot feel and high resilience performances and attains a long flight distance.
EXAMPLES
The following Examples and Comparative Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.
Examples 1 to 3 and Comparative Examples 1 to 3
In Examples 1 to 3, the following components thermoplastic resin, diene rubber and crosslinking agent were used in the amount described in Table 1 while changing the ratio of the diene rubber to the thermoplastic resin, and the mixture was subjected to dynamic crosslinking. In Comparative Examples 1 to 3, the components were used in the amount described in Table 2, and the mixture was only kneaded and were not subjected to dynamic crosslinking.
Thermoplastic Resin:
Hi-milan AM7315 (trade name, ethylene-methacrylic acid copolymer ionomer resin neutralized with a zinc ion manufactured by Mitsui Du Pont Polychemical Co., Ltd.)
Diene Rubber:
Esprene 501A (trade name, ethylene-propylene-diene rubber (EPDM) manufactured by Sumitomo Chemical Industries Co., Ltd.)
Crosslinking Agent:
Balnoc (trade name, p,p'-dibenzoylquinone dioxime manufactured by Nihon Yushi Co., Ltd.)
The dynamic crosslinking in Examples 1 to 3 was carried out with kneading the formulation materials shown in Table 1 at 180° C. at 100 rpm using a laboplast mill manufactured by Toyo Seiki Co., Ltd. Then, the sample obtained after the termination of the dynamic crosslinking was pulverized into pieces of 3 to 5 mm, which was subjected to sheet press at 170° C. for 15 minutes to give a sample for the measurement of physical properties.
The termination of the dynamic crosslinking in Examples 1 to 3 was carried out by a method comprising terminating immediately after satisfying the above ideal torque ratio and reaching the maximum torque ratio. The kneading in Comparative Examples 1 to 3 was carried out by a method comprising kneading for the same time as that required for the dynamic crosslinking in the corresponding Example.
In addition, the particle size was determined by taking a reflection electron image micrograph using a scanning electron microscope (Model T-220A, manufactured by JEOL Co.) and measuring a perpendicular length of any fifty rubber particles. The numerical value due to number average was taken as an average particle size. In addition, no dynamic crosslinking was carried out in Comparative Examples 1 to 3 and the thermoplastic resin and diene rubber form a continuous layer, respectively. Therefore, the particle size could not be measured. In addition, physical properties (tensile strength, elongation and elongation set) of the resulting crosslinked material were measured according to JIS-K6301 (Physical test method of vulcanized rubber).
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of crosslinked materials of Examples 1 to 3 are shown in Table 1. The formulation, revolution number at the time of kneading, time and physical properties of crosslinked materials of Comparative Examples 1 to 3 are shown in Table 2.
In addition, the amounts of the respective formulation materials in the respective tables are parts by weight. The thermoplastic resin and diene rubber are indicated by the trade name in the tables.
              TABLE 1                                                     
______________________________________                                    
               Example 1                                                  
                      Example 2                                           
                               Example 3                                  
______________________________________                                    
Hi-milan AM7315  80       60       30                                     
Esprene 501A     20       40       70                                     
Barium sulfate   4        8        14                                     
Stearic acid     0.2      0.4      0.7                                    
Crosslinking agent (oxime) (based                                         
                 0.4      0.8      1.4                                    
on 100 parts by weight of rubber)                                         
                 (2)      (2)      (2)                                    
Revolution number (rpm)                                                   
                 100      100      100                                    
Ideal torque ratio                                                        
                 102      104      107                                    
Maximum torque ratio                                                      
                 105      108      115                                    
Average particle size (μm)                                             
                 8        4        6                                      
Tensile strength (kg/cm.sup.2)                                            
                 235.9    158.9    97.0                                   
Elongation (%)   304      174      267                                    
Elongation set (%)                                                        
                 22.3     7.8      5.8                                    
______________________________________                                    

              TABLE 2                                                     
______________________________________                                    
           Comparative                                                    
                    Comparative                                           
                              Comparative                                 
           Example 1                                                      
                    Example 2 Example 3                                   
______________________________________                                    
Hi-milan AM7315                                                           
             80         60        30                                      
Esprene 501A 20         40        70                                      
Barium sulfate                                                            
             4          8         14                                      
Stearic acid 0.2        0.4       0.7                                     
Revolution number (rpm)                                                   
             100        100       100                                     
Time (minute)                                                             
             10         10        7                                       
Tensile strength (kg/cm.sup.2)                                            
             234.3      145.7     83.2                                    
Elongation (%)                                                            
             317        167       161                                     
Elongation set (%)                                                        
             82.4       65.0      39.0                                    
______________________________________
As is shown in Table 1, the thermoplastic elastomer compositions of Examples 1 to 3 showed a small elongation set and were superior in restoring force. That is, the physical properties vary depending on the ratio of the thermoplastic resin to the diene rubber, but the thermoplastic elastomer composition of Example 1 wherein the ratio of the thermoplastic resin is the highest showed an elongation set of 22.3%. It showed a small elongation set and was superior in restoring force to that of Comparative Example 1 wherein the formulation is the same but no crosslinking agent is contained as well as that of Comparative Example 3 wherein the ratio of the thermoplastic resin is the smallest
Example 4
According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization as the crosslinking agent, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, and physical properties thereof were measured.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked material of Example 4 are shown in Table 3. In addition the, Comparative Example which corresponds to Example 4 is Comparative Example 1 and, therefore, the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked material of Comparative Example 1 are also shown in Table 3. In addition, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
In addition, the crosslinking agent used in Example 4 is as follows.
Crosslinking Agent:
Sulfur
Vulcanization accelerator (tetrabutylthiuram disulfide, Nocceler TBT-N (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.)
              TABLE 3                                                     
______________________________________                                    
                          Comparative                                     
                  Example 4                                               
                          Example 1                                       
______________________________________                                    
Hi-milan AM7315      80        80                                         
Esprene 501A         20        20                                         
Barium sulfate       4         4                                          
Stearic acid         0.2       0.2                                        
Crosslinking agent (based on 100                                          
                     0.4 (2)   0                                          
parts by weight ot rubber)                                                
sulfur                                                                    
Vulcanization accelerator TBT-N                                           
                     0.4 (2)   0                                          
Revotution number (rpm)                                                   
                    100       100                                         
Ideal torque ratio  102       time                                        
Maximum torque ratio                                                      
                    109        10 minutes                                 
Average particle size (μm)                                             
                     1.2                                                  
Tensile strength (kg/cm.sup.2)                                            
                    249.2     234.3                                       
Elongation (%)      310       317                                         
Elongation set (%)   23.1      82.4                                       
______________________________________
As is apparent from the results shown in Table 3, the thermoplastic elastomer composition of Example 4 showed a small elongation set and was superior in restoring force to that of the corresponding Comparative Example 1. In addition, a considerable decrease in tensile strength and elongation was not observed.
Examples 5 to 6 and Comparative Examples 4 to 5
According to the same manner as that described in Example 1 except for changing the kind of the diene rubber, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Examples 5 to 6. According to the same manner as that described in Example 1 except for changing the kind of the thermoplastic resin, the mixture was only kneaded to produce a thermoplastic elastomer composition, in Comparative Examples 4 to 5. Then, their physical properties were compared.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 5 to 6 are shown in Table 4. In addition, the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked materials of Comparative Examples 4 to 5 are shown in Table 5. In addition, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
In addition, the diene rubbers used in Examples 5 to 6 and Comparative Examples 4 to 5 are as follows.
Diene Rubbers:
Esprene 301 (ethylene-propylene-diene rubber (EPDM), manufactured by Sumitomo Chemical Industries Co., Ltd.)
Nodel 1470 (ethylene-propylene-diene rubber (EPDM), manufactured by Showa Denko Co., Ltd.)
              TABLE 4                                                     
______________________________________                                    
                  Example 5                                               
                         Example 6                                        
______________________________________                                    
Hi-milan AM7315     80       60                                           
Esprene 301         20       0                                            
Nodel 1470          0        20                                           
Barium sulfate      4        4                                            
Stearic acid        0.2      0.2                                          
Crosslinking agent (oxime) (based                                         
                    0.4      0.4                                          
on 100 parts by weight of rubber)                                         
                    (2)      (2)                                          
Revolution number (rpm)                                                   
                    100      100                                          
Ideal torque ratio  102      102                                          
Maximum torque ratio                                                      
                    105      104                                          
Average particle size (μm)                                             
                    10       9                                            
Tensile strength (kg/cm.sup.2)                                            
                    228.3    190.8                                        
Elongation (%)      267      253                                          
Elongation set (%)  25.4     29.9                                         
______________________________________                                    

              TABLE 5                                                     
______________________________________                                    
               Comparative                                                
                       Comparative                                        
               Example 4                                                  
                       Example 5                                          
______________________________________                                    
Hi-milan AM7315  80        80                                             
Esprene 301      20        0                                              
Nodel 1470       0         20                                             
Barium sulfate   4         4                                              
Stearic acid     0.2       0.2                                            
Revolution number (rpm)                                                   
                 100       100                                            
Time (minute)    10        10                                             
Tensile strength (kg/cm.sup.2)                                            
                 190.2     198.8                                          
Elongation (%)   216       250                                            
Elongation set (%)                                                        
                 78.5      85.1                                           
______________________________________
As is apparent from the results shown in Tables 4 and 5, the thermoplastic elastomer compositions of Examples 5 to 6 showed a small elongation set and were superior in restoring force to those of Comparative Examples 4 to 5. In addition, a considerable decrease in tensile strength and elongation was not observed.
Examples 7 to 8 and Comparative Examples 6 to 7
According to the same manner as that described in Example 1 except for using a butadiene rubber as the diene rubber and changing the amount thereof, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Examples 7 to 8. According to the same manner as that described in Example 1 except for using a butadiene rubber as the diene rubber and changing the amount thereof, the mixture was only kneaded to produce a thermoplastic elastomer composition, in Comparative Examples 6 to 7. Then, their physical properties were compared.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 7 to 8 are shown in Table 6. In addition, the formulation amount, revolution number at the time of kneading, time and physical properties of the crosslinked materials of Comparative Examples 6 to 7 are shown in Table 7. In addition, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
In addition, the diene rubber used in Examples 7 to 8 and Comparative Examples 6 to 7 is as follows.
Diene Rubber:
BR01 (Hi-cis butadiene rubber, manufactured by Nihon Synthetic Rubber Co., Ltd.)
              TABLE 6                                                     
______________________________________                                    
                  Example 7                                               
                         Example 8                                        
______________________________________                                    
Hi-milan AM7315     80       60                                           
BR01                20       40                                           
Barium sulfate      4        8                                            
Stearic acid        0.2      0.4                                          
Crosslinking agent (oxime) (based                                         
                    0.4      0.8                                          
on 100 parts by weight of rubber)                                         
                    (2)      (2)                                          
Revolution number (rpm)                                                   
                    100      100                                          
Ideal torque ratio  102      104                                          
Maximum torque ratio                                                      
                    104      107                                          
Average particle size (μm)                                             
                    8        4                                            
Tensile strength (kg/cm.sup.2)                                            
                    223.7    190.0                                        
Elongation (%)      307      365                                          
Elongation set (%)  30.2     27.2                                         
______________________________________                                    

              TABLE 7                                                     
______________________________________                                    
               Comparative                                                
                       Comparative                                        
               Example 6                                                  
                       Example 7                                          
______________________________________                                    
Hi-milan AM7315  80        60                                             
BR01             20        40                                             
Barium sulfate   4         8                                              
Stearic acid     0.2       0.4                                            
Revolution number (rpm)                                                   
                 100       100                                            
Time (minute)    8         8                                              
Tensile strength (kg/cm.sup.2)                                            
                 193.5     162.5                                          
Elongation (%)   225       235                                            
Elongation set (%)                                                        
                 80.3      70.5                                           
______________________________________
As is apparent from the results shown in Tables 6 and 7, the thermoplastic elastomer compositions of Examples 7 to 8 showed a small elongation set and were superior in restoring force to those of Comparative Examples 6 to 7. In addition, a considerable decrease in tensile strength and elongation was not observed, and they were rather superior.
Examples 9 to 10
According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization accelerator, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition. Then, their physical properties were measured.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 9 to 10 are shown in Table 8. In addition, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 1.
In addition, the crosslinking agent used in Examples 9 to 10 is as follows.
Crosslinking Agent:
Sulfur
Vulcanization accelerator (tetrabutylthiuram disulfide, Nocceler TT (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.)
              TABLE 8                                                     
______________________________________                                    
                  Example 9                                               
                          Example 10                                      
______________________________________                                    
Hi-milan AM7315      80        60                                         
BR01                 20        40                                         
Barium sulfate       4         8                                          
Stearic acid         0.2       0.4                                        
Crosslinking agent (oxime) based                                          
on 100 parts by weight of rubber)                                         
Sulfur               0.4 (2)   0.8 (2)                                    
Vulcanization accelerator TT                                              
                     0.4 (2)   0.8 (2)                                    
Revolution number (rpm)                                                   
                    100       100                                         
Ideal torque ratio  102       104                                         
Maximum torque ratio                                                      
                    106       110                                         
Average particle size (μm)                                             
                     2.1       0.9                                        
Tensile strength (kg/cm.sup.2)                                            
                    241.2     203.8                                       
Elongation (%)      291       311                                         
Elongation set (%)   31.6      24.9                                       
______________________________________
Comparative Examples corresponding to Examples 9 to 10 are Comparative Examples 6 to 7. As is apparent from the results shown in Tables 8 and 7, the thermoplastic elastomer compositions of Examples 9 to 10 showed a small elongation set and were superior in restoring force to those of Comparative Examples 6 to 7. In addition, a considerable decrease in tensile strength and elongation was not observed.
Example 11 and Comparative Example 8
According to the same manner as that described in Example 1 except for changing the revolution number at the time of dynamic crosslinking (changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Example 11. According to the same manner as that described in Comparative Example 1 except for changing the revolution number at the time of kneading (changing from 100 rpm to 150 rpm), the mixture was kneaded to produce a thermoplastic elastomer composition, in Comparative Example 8. In Example 11, a change in average particle size of crosslinked diene rubber particles and that in physical properties were examined. In Comparative Example 8, a change in physical properties was examined.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked material of Example 11 as well as formulation, revolution number at the time of kneading, time and physical properties of the crosslinked material of Comparative Example 8 are shown in Table 9. In addition, the indicating method, and measuring method of the particle size and physical properties are the same as those of Example 1.
              TABLE 9                                                     
______________________________________                                    
                          Comparative                                     
                  Example 11                                              
                          Example 8                                       
______________________________________                                    
Hi-milan AM7315     80        80                                          
Esprene 501A        20        20                                          
Barium sulfate      4         4                                           
Stearic acid        0.2       0.2                                         
Crosslinking agent (oxime) (based                                         
                    0.4       0                                           
on 100 parts by weight of rubber)                                         
                    (2)       (0)                                         
Revolution number (rpm)                                                   
                    150       150                                         
Ideal torque ratio  102       time                                        
Maximum torque ratio                                                      
                    107       8 minutes                                   
Average particle size (μm)                                             
                    3         --                                          
Tensile strength (kg/cm.sup.2)                                            
                    205.0     192.3                                       
Elongation (%)      189       168                                         
Elongation set (%)  13.7      70.7                                        
______________________________________
As is shown in Table 9, the thermoplastic elastomer composition of Example 11 showed a small elongation set and was superior in restoring force to that of Comparative Example 8. In addition, a considerable decrease in tensile strength and elongation was not admitted observed, and they were rather superior.
The thermoplastic elastomer composition of Example 11 was compared with that of Example 11. As a result, the average particle size of crosslinked diene rubber particles became small from 8 μm to 3 μm and, at the same time, the elongation set became small from 22.3% to 13.7%. On the other hand, in Comparative Examples 8 and 1, the elongation set became small but the tensile strength and elongation were lowered.
Example 12
According to the same manner as that described in Example 1 except for changing the kind of the crosslinking agent and using sulfur and a vulcanization accelerator according to the same manner as that described in Example 4 except for changing the revolution number at the time of dynamic crosslinking (i.e. changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition. Then, a change in average particle size of crosslinked diene rubber particles and that in physical properties were examined.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio of Example 12 are shown in Table 10. Since Comparative Example corresponding to Example 12 is Comparative Example 8, the average particle size of crosslinked diene rubber particles and physical properties of the crosslinked material as well as formulation, revolution number at the time of kneading, time and physical properties of Comparative Example 8 are shown in Table 10. In addition, the indicating method and measuring method of the particle size and physical properties are the same as those of Example 1.
In addition, the crosslinking agent used in Example 12 is as follows.
Crosslinking Agent:
Sulfur
Vulcanization accelerator (tetrabutylthiuram disulfide, Nocceler TBT-N (trade name), manufactured by Ohuchi Shinko Kagaku Kogyo Co., Ltd.)
              TABLE 10                                                    
______________________________________                                    
                          Comparative                                     
                 Example 12                                               
                          Example 8                                       
______________________________________                                    
Hi-milan AM7315     80         80                                         
Esprene 501A        20         20                                         
Barium sulfate      4          4                                          
Stearic acid        0.2        0.2                                        
Crosslinking agent (based on 100                                          
parts by weight of rubber)                                                
Sulfur              0.4 (2)    0                                          
Vulcanization accelerator TBT-N                                           
                    0.4 (2)    0                                          
Revolution number (rpm)                                                   
                   150        150                                         
Ideal torque ratio 102        Time                                        
Maximum torque ratio                                                      
                   111        8 minutes                                   
Average particle size (μm)                                             
                    0.7       --                                          
Tensile strength (kg/cm.sup.2)                                            
                   238.7      192.3                                       
Elongation (%)     300        168                                         
Elongation set (%)  16.7       70.7                                       
______________________________________
As is shown in Table 10, the thermoplastic elastomer composition of Example 12 showed a small elongation set and was superior in restoring force to that of Comparative Example 8. In addition, a considerable decrease in tensile strength and elongation was not observed, and they were rather superior.
The thermoplastic elastomer composition of Example 12 was compared with that of Example 4. As a result, the average particle size of crosslinked diene rubber particles became small from 1.2 μm to 0.7 μm and, at the same time, the elongation set became small from 23.1% to 16.7%.
Examples 13 to 15 and Comparative Examples 9 to 11
According to the same manner as that described in Example 1 except for changing the amount of the crosslinking agent, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Examples 13 to 15. According to the same manner as that described in Example 1 except for changing the amount of the crosslinking agent and torque value beyond the range of the present invention, the mixture was subjected to dynamic crosslinking to produce a thermoplastic elastomer composition, in Comparative Examples 9 to 10. In addition, physical properties of the thermoplastic resin Hi-milan AM7315 (trade name, ionomer resin) alone are shown in Comparative Example 11.
The formulation, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Examples 13 to 15 are shown in Table 11. The formulation amount, revolution number at the time of dynamic crosslinking, ideal torque ratio and maximum torque ratio, average particle size of crosslinked diene rubber particles and physical properties of the crosslinked materials of Comparative Examples 9 to 10 are shown in Table 11. In addition, the indicating method and measuring method of the particle size and physical properties are the same as those of Example 1.
              TABLE 11                                                    
______________________________________                                    
               Example                                                    
                      Example  Example                                    
               13     14       15                                         
______________________________________                                    
Hi-milan AM7315  80       80       80                                     
Esprene 501A     20       20       20                                     
Barium sulfate   4        4        4                                      
Stearic acid     0.2      0.2      0.2                                    
Crosslinking agent (oxime) (based                                         
                 0.04     1        2                                      
on 100 parts by weight of rubber)                                         
                 (0.2)    (5)      (10)                                   
Revolution number (rpm)                                                   
                 100      100      100                                    
Ideal torque ratio                                                        
                 102      102      102                                    
Maximum torque ratio                                                      
                 103      107      112                                    
Average particle size (μm)                                             
                 7        9        10                                     
Tensile strength (kg/cm.sup.2)                                            
                 241.1    219.9    200.5                                  
Elongation (%)   309      284      277                                    
Elongation set (%)                                                        
                 20.7     25.0     30.3                                   
______________________________________                                    

              TABLE 12                                                    
______________________________________                                    
            Comparative                                                   
                    Comparative                                           
                              Comparative                                 
            Example 9                                                     
                    Example 10                                            
                              Example 11                                  
______________________________________                                    
Hi-milan AM7315                                                           
              80        80        100                                     
Esprene 501A  20        20        0                                       
Barium sulfate                                                            
              4         4         0                                       
Stearic acid  0.2       0.2       0                                       
Crosslinking agent                                                        
              0.01      3         0                                       
(oxime) (based on 100                                                     
              (0.05)    (15)      0                                       
parts by weight of rubber)                                                
Revolution number (rpm)                                                   
              100       100       --                                      
Ideal torque ratio                                                        
              102       102       --                                      
Maximum torque ratio                                                      
              101       120       --                                      
Average particle size (μm)                                             
              18        16        --                                      
Tensile strength (kg/cm.sup.2)                                            
              164.9     139.8     204.0                                   
Elongation (%)                                                            
              233       219       151                                     
Elongation set (%)                                                        
              72.2      54.8      97.3                                    
______________________________________
As is apparent from the results shown in Tables 11 and 12, the thermoplastic elastomer compositions of Examples 13 to 15 showed a small elongation set and were superior in restoring force to those of Comparative Examples 9 to 10. In addition, they had the same or better characteristics (e.g. tensile strength, elongation, etc.) as that of Comparative Example 11 using the thermoplastic resin alone.
Examples 16 to 18 and Comparative Examples 12 to 14
Two-piece solid golf balls of Examples 16 to 18 and Comparative Examples 12 to 14 were made by allowing to go through the processes shown in the following items (1) to (3).
(1) Preparation of Core:
A rubber composition prepared by formulating 25 parts by weight of zinc acrylate, 23 parts by weight of zinc oxide and 1 part by weight of dicumyl peroxide in 100 parts by weight of BR01 (trade name, butadiene rubber manufactured by Nihon Synthetic Rubber Co., Ltd.) was put in a mold and subjected to heat molding under pressure at 155° C. for 30 minutes to make a core having a diameter of 38.5 mm.
(2) Preparation of cover Composition:
In Examples 16 to 18, the following ionomer resin, diene rubber and crosslinking agent were used in the amount described in Table 13 while changing a ratio of the diene rubber to the ionomer resin, and the mixture was subjected to dynamic crosslinking. In Comparative Examples 12 to 14, they were used in the amount described in Table 14, and the mixture was only kneaded.
Ionomer Resin:
Hi-milan AM7315 (trade name, ethylene-methacrylic acid copolymer ionomer resin neutralized with a zinc ion manufactured by Mitsui Du Pont Polychemical Co., Ltd.)
Diene Rubber:
Esprene 501(trade name, ethylene-propylene-diene rubber (EPDM) manufactured by Sumitomo Chemical Industries Co., Ltd.)
Crosslinking Agent:
Balnoc DGM (trade name, p,p'-dibenzoylquinone dioxime manufactured by Nihon Yushi Co., Ltd.)
The dynamic crosslinking in Examples 16 to 18 was carried out while kneading the formulation materials shown in Table 13 at 180° C. at 100 rpm using a laboplast mill manufactured by Toyo Seiki Co., Ltd. The kneading of the formulation materials shown in Table 14 in Comparative Examples 12 to 14 was carried out at 100 rpm using the same laboplast mill manufactured by Toyo Seiki Co., Ltd. Incidentally, since no crosslinking is formulated in Comparative Examples 12 to 14, no dynamic crosslinking of the diene rubber arises.
The termination of the dynamic crosslinking in Examples 16 to 18 was carried out by a method comprising terminating immediately after satisfying the above ideal torque ratio and reaching the maximum torque ratio. The kneading in Comparative Examples 12 to 14 was carried out by a method comprising kneading for the same time as that required for the dynamic crosslinking in the corresponding Example.
In addition, the amounts of the respective formulation materials in the respective tables are parts by weight. The thermoplastic resin and diene rubber are indicated by the trade name in the tables.
(3) Preparation of Golf Ball:
A two-piece solid golf ball having an outer diameter of 42.7 mm was made by pulverizing the cover composition of the above (2) into pieces of 3 to 5 mm, molding them to form a half-shell, covering the core of the above (1) using two half-shells, followed by heat molding at 160° C. for 3 minutes.
The weight, resilience coefficient and flight distance of the resulting golf ball were measured and the shot feel was determined. The measuring method of the resilience coefficient and flight distance as well as evaluation method of the shot feel were as follows.
Measuring Method of Resilience Coefficient:
A stainless steel column (198 g) is launched at an initial velocity of 35 m/second using an air gun to strike it against a golf ball ahead of the column. Then, the velocity of the column and golf ball before and after striking is measured, respectively, using two photoelectric tubes to calculate a resilience coefficient from each velocity and weight. The above measurement is carried out as to eight golf balls and the average value is taken as the value of the resilience coefficient.
Measuring Method of Flight Distance:
A golf ball (n=8) is hit with a No. 1 wood club at a head speed of 45 m/second using a swing robot manufactured by True Temper Co., and the distance to the drop point is measured. The results are shown by the average value.
Evaluation Method of Shot Feel:
A golf ball is practically hit with a No. 1 wood club by 5 top professional golfers and shot feel is evaluated according to the following seven-grade criteria.
HH: Too hard
H: Hard
AH: Slightly hard but within a good range
A: Good
AS: Slightly soft but within a good range
S: Soft
SS: Too soft
In addition, the particle size of crosslinked diene rubber particles of the thermoplastic elastomer used for the cover was carried out by the following method.
Firstly, a sample for measurement was made by pulverizing the cover composition of the above (2) into pieces of 3 to 5 mm and subjecting to heat molding under pressure at 160° C. for 3 minutes to form a sheet. In addition, the particle size was determined by taking a reflection electron image micrograph using a scanning electron microscope (Model T-220A, manufactured by JEOL Co.) and measuring a perpendicular length of any fifty rubber particles. The numerical value due to number average was taken as an average particle size. In addition, no dynamic crosslinking was carried out in Comparative Examples 12 to 14 and the thermoplastic resin and diene rubber form a continuous layer, respectively. Therefore, the particle size could not be measured.
The formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as weight, resilience coefficient, flight distance and evaluation results of the shot feel of the resulting golf balls of Examples 16 to 18 are shown in Table 13. The formulation of the cover composition, revolution number at the time of kneading and time as well as weight, resilience coefficient, flight distance and evaluation results of the shot feel of the resulting golf balls of Comparative Examples 12 to 14 are shown in Table 14.
              TABLE 13                                                    
______________________________________                                    
             Example 16                                                   
                     Example 17                                           
                               Example 18                                 
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315                                                           
               100       100       100                                    
Esprene 501A   10        25        50                                     
Barium sulfate 2         5         10                                     
Stearic acid   0.1       0.25      0.5                                    
Crosslinking agent                                                        
               0.2       0.5       1.0                                    
(based on 100 parts by weight                                             
               (2)       (2)       (2)                                    
of rubber)                                                                
Revolution number (rpm)                                                   
               100       100       100                                    
Ideal torque ratio                                                        
               101       102       103                                    
Maximum torque ratio                                                      
               102       104       107                                    
Average particle size (μm)                                             
               6         7         10                                     
Ball characteristics                                                      
Weight (g)     45.3      45.4      45.4                                   
Resilience coefficient                                                    
               0.8362    0.8255    0.8178                                 
Flight distance (yard)                                                    
               227       225       224                                    
Shot feel      A         AS        AS                                     
______________________________________                                    

              TABLE 14                                                    
______________________________________                                    
             Example 12                                                   
                     Example 13                                           
                               Example 14                                 
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315                                                           
               100       100       100                                    
Esprene 501A   10        25        50                                     
Barium sulfate 2         5         10                                     
Stearic acid   0.1       0.25      0.5                                    
Revolution number (rpm)                                                   
               100       100       100                                    
Time (minute)  10        7         7                                      
Ball characteristics                                                      
Weight (g)     45.3      45.3      45.3                                   
Resilience coefficient                                                    
               0.8016    0.7955    0.7821                                 
Flight distance (yard)                                                    
               220       219       216                                    
Shot feel      S         SS        SS                                     
______________________________________
As is apparent from the results shown in Tables 13 and 14, the golf balls of Examples 16 to 18 showed a large resilience coefficient and long flight distance and were also superior in shot feel to those of Comparative Examples 12 to 14 wherein the formulation is the same but no crosslinking agent is contained.
Examples 19 to 20 and Comparative Examples 15 to 16
According to the same manner as that described in Example 16 except for changing the kind of the diene rubber, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 19 to 20. According to the same manner as that described in Example 16 except for changing the kind of the diene rubber, the mixture was only kneaded to prepare a cover composition, in Comparative Examples 15 to 16. Then, their characteristics were evaluated.
In addition, the diene rubbers used in Examples 19 to 20 and Comparative Examples 15 to 16 are as follows.
Diene Rubbers:
Esprene 301 (ethylene-propylene-diene rubber (EPDM), manufactured by Sumitomo Chemical Industries Co., Ltd.)
Nodel 1470 (ethylene-propylene-diene rubber (EPDM), manufactured by Showa Denko Co., Ltd.)
The formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as characteristics of the resulting golf balls of Examples 19 to 20 are shown in Table 15. In addition, the formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 15 to 16 are shown in Table 16. In addition, the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
              TABLE 15                                                    
______________________________________                                    
                Example 19                                                
                        Example 20                                        
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315   100       100                                           
Esprene 301       25        0                                             
Nodel 1470        0         25                                            
Barium sulfate    5         5                                             
Stearic acid      0.25      0.25                                          
Crosslinking agent                                                        
                  0.5       0.5                                           
(based on 100 parts by                                                    
                  (2)       (2)                                           
weight of rubber)                                                         
Revolution number (rpm)                                                   
                  100       100                                           
Ideal torque ratio                                                        
                  102       102                                           
Maximum torque ratio                                                      
                  104       104                                           
Average particle size (μm)                                             
                  8         7                                             
Ball characteristics                                                      
Weight (g)        45.3      45.4                                          
Resilience coefficient                                                    
                  0.8213    0.8222                                        
Flight distance (yard)                                                    
                  224       225                                           
Shot feel         AS        AS                                            
______________________________________                                    

              TABLE 16                                                    
______________________________________                                    
               Comparative                                                
                       Comparative                                        
               Example 15                                                 
                       Example 16                                         
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315  100       100                                            
Esprene 301      25        0                                              
Nodel 1470       0         25                                             
Barium sulfate   5         5                                              
Stearic acid     0.25      0.25                                           
Revolution number (rpm)                                                   
                 100       100                                            
Time (minute)    7         7                                              
Ball characteristics                                                      
Weight (g)       45.2      45.4                                           
Resilience coefficient                                                    
                 0.8023    0.8040                                         
Flight distance (yard)                                                    
                 220       221                                            
Shot feel        SS        S                                              
______________________________________
As is apparent from the results shown in Tables 15 and 16, the golf balls of Examples 19 to 20 showed a large resilience coefficient and long flight distance and were also superior in shot feel to those of Comparative Examples 15 to 16.
Examples 21 to 22 and Comparative Examples 17 to 18
According to the same manner as that described in Example 16 except for using a butadiene rubber as the diene rubber while changing the amount, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 21 to 22. According to the same manner as that described in Example 16 except for using a butadiene rubber as the diene rubber while changing the amount, the mixture was only kneaded to prepare a cover composition, in Comparative Examples 17 to 18. Then, their characteristics were measured.
In addition, the diene rubbers used in Examples 21 to 22 and Comparative Examples 17 to 18 are as follows.
Diene Rubber:
BR01 (Hi-cis butadiene rubber (EPDM), manufactured by Nihon Synthetic Rubber Co., Ltd.)
The formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles of as well as characteristics of the resulting golf balls of Examples 21 to 22 are shown in Table 17. In addition, the formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 17 to 18 are shown in Table 18. In addition the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
              TABLE 17                                                    
______________________________________                                    
                Example 21                                                
                        Example 22                                        
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315   100       100                                           
BR01              25        50                                            
Barium sulfate    5         10                                            
Stearic acid      0.25      0.5                                           
Crosslinking agent                                                        
                  0.5       1                                             
(based on 100 parts by                                                    
                  (2)       (2)                                           
weight of rubber)                                                         
Revolution number (rpm)                                                   
                  100       100                                           
Ideal torque ratio                                                        
                  102       103                                           
Maximum torque ratio                                                      
                  107       112                                           
Average particle size (μm)                                             
                  7         8                                             
Ball characteristics                                                      
Weight (g)        45.5      45.4                                          
Resilience coefficient                                                    
                  0.8301    0.8282                                        
Flight distance (yard)                                                    
                  226       225                                           
Shot feel         AS        AS                                            
______________________________________                                    

              TABLE 18                                                    
______________________________________                                    
               Comparative                                                
                       Comparative                                        
               Example 17                                                 
                       Example 18                                         
______________________________________                                    
Cover composilion                                                         
Hi-milan AM7315  100       100                                            
BR01             25        50                                             
Barium sulfate   5         10                                             
Stearic acid     0.25      0.5                                            
Revolution number (rpm)                                                   
                 100       100                                            
Time (minute)    7         7                                              
Ball characteristics                                                      
Weight (g)       45.3      45.3                                           
Resilience coefficient                                                    
                 0.7991    0.7863                                         
Flight distance (yard)                                                    
                 219       217                                            
Shot feel        S         SS                                             
______________________________________
As is apparent from the results shown in Tables 17 and 18, the golf balls of Examples 21 to 22 showed a large resilience coefficient and long flight distance and were also superior in shot feel to those of Comparative Examples 17 to 18.
Example 23 and Comparative Example 19
According to the same manner as that described in Example 16 except for changing the revolution number at the time of dynamic crosslinking (changing from 100 rpm to 150 rpm), the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Example 23. According to the same manner as that described in Example 12 except for changing the revolution number at the time of kneading (changing from 100 rpm to 150 rpm), the mixture was only kneaded to prepare a cover composition, in Comparative Example 19. Then, their characteristics were measured.
The formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio, average particle size of crosslinked diene rubber particles and characteristics of the resulting golf ball of Example 23 as well as formulation of the cover composition, revolution number at the time of kneading, time and characteristics of the resulting golf ball of Comparative Example 19 are shown in Table 19 respectively. In addition, the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
              TABLE 19                                                    
______________________________________                                    
                        Comparative                                       
                Example 23                                                
                        Example 19                                        
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315   100       100                                           
Esprene 501A      25        25                                            
Barium sulfate    5         5                                             
Stearic acid      0.25      0.25                                          
Crosslinking agent                                                        
                  0.5       0                                             
(based on 100 parts by                                                    
                  (2)       (0)                                           
weight of rubber)                                                         
Revolution number (rpm)                                                   
                  150       150                                           
Ideal torque ratio                                                        
                  102       --                                            
Maximum torque ratio                                                      
                  107       --                                            
Time (minute)     7         7                                             
Average particle size (μm)                                             
                  2         --                                            
Ball characteristics                                                      
Weight (g)        45.4      45.4                                          
Resilience coefficient                                                    
                  0.8370    0.7964                                        
Flight distance (yard)                                                    
                  227       219                                           
Shot feel         AS        SS                                            
______________________________________
As shown in Table 19, the golf ball of Example 23 showed a large resilience coefficient and long flight distance and was also superior in shot feel to that of Comparative Example 19.
In addition, the golf ball of Example 23 was compared with that of Example 16. As a result, the average particle size of crosslinked diene rubber particles became small from 6 μm to 2 μm and, at the same time, the resilience coefficient and flight distance were improved. On the other hand, the resilience coefficient of the golf ball of Comparative Example 19 is slightly smaller than that of Comparative Example 12, and the shot feel became inferior.
Examples 24 to 25 and Comparative Examples 20 to 22
According to the same manner as that described in Example 16 except for changing the amount of the crosslinking agent, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Examples 24 to 25. According to the same manner as that described in Example 16 except for changing the amount of the crosslinking agent beyond the range of the present invention, the mixture was subjected to dynamic crosslinking to prepare a cover composition, in Comparative Examples 20 to 21. In Comparative Example 21, Hi-milan AM7315 (trade name, ionomer resin) alone was used as the cover composition to make a golf ball, and characteristics were evaluated.
The formulation of the cover composition, revolution number at the time of dynamic crosslinking, ideal torque ratio, maximum torque ratio and average particle size of crosslinked diene rubber particles as well as characteristics of the resulting golf balls of Examples 24 to 25 are shown in Table 20. The formulation of the cover composition, revolution number at the time of kneading and time as well as characteristics of the resulting golf balls of Comparative Examples 20 to 21 and ball characteristics of Comparative Example 22 are shown in Table 21. In addition, the core used, the indicating method, dynamic crosslinking method and measuring method of the particle size and physical properties are the same as those of Example 16.
              TABLE 20                                                    
______________________________________                                    
                Example 24                                                
                        Example 25                                        
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315   100       100                                           
Esprene 501A      25        25                                            
Barium sulfate    5         5                                             
Stearic acid      0.25      0.25                                          
Crosslinking agent                                                        
                  0.05      2.5                                           
(based on 100 parts by                                                    
                  (0.2)     (10)                                          
weight of rubber)                                                         
Revolution number (rpm)                                                   
                  100       100                                           
Ideal torque ratio                                                        
                  102       102                                           
Maximum torque ratio                                                      
                  103       108                                           
Average particle size (μm)                                             
                  7         6                                             
Ball characteristics                                                      
Weight (g)        45.4      45.3                                          
Resilience coefficient                                                    
                  0.8215    0.8179                                        
Flight distance (yard)                                                    
                  224       224                                           
Shot feel         AS        AS                                            
______________________________________                                    

              TABLE 21                                                    
______________________________________                                    
            Comparative                                                   
                    Comparative                                           
                              Comparative                                 
            Example 20                                                    
                    Example 21                                            
                              Example 22                                  
______________________________________                                    
Cover composition                                                         
Hi-milan AM7315                                                           
              100       100       100                                     
Esprene 501A  25        25        0                                       
Barium sulfate                                                            
              5         5         0                                       
Stearic acid  0.25      0.25      0                                       
Crosslinking agent                                                        
              0.0125    3         0                                       
(based on 100 parts by                                                    
              (0.05)    (12)      0                                       
weight of rubber)                                                         
Revolution number (rpm)                                                   
              100       100       --                                      
Ideal torque ratio                                                        
              102       102       --                                      
Maximum torque ratio                                                      
              101       115       --                                      
Average particle size (μm)                                             
              16        14        --                                      
Ball characteristics                                                      
Weight (g)    45.4      45.5      45.3                                    
Resilience coefficient                                                    
              0.8033    0.8041    0.8049                                  
Flight distance (yard)                                                    
              220       221       221                                     
Shot feel     S         S         HH                                      
______________________________________
As is apparent from the results shown in Tables 20 and 21, the golf balls of Examples 24 to 25 showed a large resilience coefficient and flight distance and were also superior in shot feel to those of Comparative Examples 20 to 22.

Claims (11)

What is claimed is:
1. A thermoplastic elastomer composition comprising a thermoplastic resin and crosslinked diene rubber particles having an average diameter of not more than 10 μm dispersed in the thermoplastic resin, wherein the thermoplastic resin is an ethylene-acrylic acid copolymer neutralized with a metal ion, an ethylene-methacrylic acid copolymer neutralized with a metal ion or an ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion; said elastomer composition being prepared by dispersing the diene rubber in the thermoplastic resin to form a mixture in a mixing device, calculating the actual torque value of the mixing device, dynamically crosslinking the diene rubber with a crosslinking agent in the mixing device and then terminating the dynamic crosslinking immediately upon reaching the ideal torque value B defined by the equation:
B=100+(10×A)
wherein A is defined as ##EQU2## provided that (i) the actual torque before dynamic crosslinking is calculated on the basis of 100×; and (ii)
crosslinking is terminated prior to reaching maximum torque.
2. The thermoplastic elastomer composition according to claim 1, wherein the diene rubber is an ethylene-propylene-diene rubber.
3. The thermoplastic elastomer composition according to claim 1, wherein the diene rubber is a butadiene rubber.
4. The thermoplastic elastomer composition according to claim 1, wherein the crosslinking is an oxime crosslinking agent.
5. The thermoplastic elastomer composition according to claim 1, wherein the crosslinking agent is a mixture of sulfur and a vulcanization accelerator.
6. A process for producing a thermoplastic elastomer composition, which comprises dispersing a diene rubber in a thermoplastic resin, to form a mixture in a mixing device, calculating the actual torque value of the mixing device, dynamically crosslinking the diene rubber with a crosslinking agent in the mixing device and then terminating the dynamic crosslinking immediately upon reaching the ideal torque value B defined by the equation
B=100+(10×A)
wherein A is defined as ##EQU3## provided that (i) the actual torque before dynamic crosslinking is calculated on the basis of 100, and (ii) crosslinking is terminated prior to reaching maximum torque so as to disperse crosslinked diene rubber particles having an average particle size of not more than 10 μm in the thermoplastic resin, and wherein the thermoplastic resin is an ethylene-acrylic acid copolymer neutralized with a metal ion, or an ethylene-methacrylic acid copolymer neutralized with a metal ion or an ethylene-acrylic acid-methacrylic acid terpolymer neutralized with a metal ion.
7. A golf ball comprising a core and a cover covering the core, wherein said cover comprises, as base polymer, a thermoplastic elastomer composition according to claim 1.
8. The golf ball according to claim 7, wherein the diene rubber is an ethylene-propylene-diene rubber.
9. The golf ball according to claim 7, wherein the diene rubber is a butadiene rubber.
10. The golf ball according to claim 7, wherein the crosslinking is an oxime crosslinking agent.
11. The golf ball according to claim 7, wherein the crosslinking agent is a mixture of sulfur and a vulcanization accelerator.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6361453B1 (en) * 1999-06-21 2002-03-26 Bridgestone Sports Co., Ltd. Solid golf ball
US6508725B1 (en) * 2001-04-18 2003-01-21 Taylor Made Golf Company, Inc. Golf ball composition and method of manufacture
US20030045638A1 (en) * 2000-06-15 2003-03-06 Jinliang Qiao Fully cured thermoplastic elastomer, process for its manufacture and applications thereof
US6562906B2 (en) 2000-08-11 2003-05-13 E. I. Du Pont De Nemours And Company Bi-modal ionomers
US6599983B2 (en) * 1997-08-20 2003-07-29 The Yokohama Rubber Co., Ltd. Golf ball, golf ball cover material composition and method of manufacturing the composition
US6645089B2 (en) * 2000-08-01 2003-11-11 Sumitomo Rubber Industries, Ltd. Golf ball
US20040132552A1 (en) * 2002-09-27 2004-07-08 Chen John Chu Golf balls with soft, resilient bimodal ionomeric covers
US20040242802A1 (en) * 2001-04-13 2004-12-02 Voorheis Peter R. Golf ball compositions comprising dynamically vulcanized blends of highly neutralized polymers and diene rubber
US7144958B2 (en) 2003-05-21 2006-12-05 E. I. Du Pont De Nemours And Company Articles prepared from compositions modified with organic fiber micropulp
US20080081710A1 (en) * 2006-10-03 2008-04-03 John Chu Chen Phase transition golf ball and method of use
US20110143864A1 (en) * 2001-11-28 2011-06-16 Sullivan Michael J Polybutadiene rubber / ionomer blends for golf balls having dual cores and covers
US20110143863A1 (en) * 2008-01-10 2011-06-16 Sullivan Michael J Golf balls having dual cores made of polybutadiene rubber / ionomer blends
US8193283B2 (en) 2000-08-11 2012-06-05 E. I. Du Pont De Nemours And Company Golf balls with soft, resilient bimodal ionomeric covers
US9102825B2 (en) 2013-09-17 2015-08-11 Nike, Inc. Dynamically crosslinked thermoplastic material process
US9328224B2 (en) 2013-09-17 2016-05-03 Nike, Inc. Dynamically crosslinked thermoplastic material process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037954A (en) * 1958-12-15 1962-06-05 Exxon Research Engineering Co Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber
US4591615A (en) * 1984-02-28 1986-05-27 The British Petroleum Company P.L.C. Thermoplastic elastomer composition
US4829124A (en) * 1986-11-17 1989-05-09 Armstrong World Industries, Inc. Dynamically crosslinked thermoplastic elastomer
US4851468A (en) * 1984-12-10 1989-07-25 Exxon Research & Engineering Company Dynamically cured thermoplastic olefin polymers
US4920177A (en) * 1989-06-20 1990-04-24 E. I. Du Pont De Nemours And Company Accelerated cure of thermoplastic compositions
US5021500A (en) * 1988-10-28 1991-06-04 Exxon Chemical Company Dynamically vulcanized alloys of crystalline polyolefin resin and halobutyl rubber material
US5407998A (en) * 1992-09-01 1995-04-18 Sumitomo Rubber Industries, Ltd. Golf ball and method for the production thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037954A (en) * 1958-12-15 1962-06-05 Exxon Research Engineering Co Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber
US4591615A (en) * 1984-02-28 1986-05-27 The British Petroleum Company P.L.C. Thermoplastic elastomer composition
US4851468A (en) * 1984-12-10 1989-07-25 Exxon Research & Engineering Company Dynamically cured thermoplastic olefin polymers
US4829124A (en) * 1986-11-17 1989-05-09 Armstrong World Industries, Inc. Dynamically crosslinked thermoplastic elastomer
US5021500A (en) * 1988-10-28 1991-06-04 Exxon Chemical Company Dynamically vulcanized alloys of crystalline polyolefin resin and halobutyl rubber material
US4920177A (en) * 1989-06-20 1990-04-24 E. I. Du Pont De Nemours And Company Accelerated cure of thermoplastic compositions
US5407998A (en) * 1992-09-01 1995-04-18 Sumitomo Rubber Industries, Ltd. Golf ball and method for the production thereof

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6599983B2 (en) * 1997-08-20 2003-07-29 The Yokohama Rubber Co., Ltd. Golf ball, golf ball cover material composition and method of manufacturing the composition
US20030216520A1 (en) * 1997-08-20 2003-11-20 The Yokohama Rubber Co., Ltd. Golf ball, golf ball cover material composition and method of manufacturing the composition
US6361453B1 (en) * 1999-06-21 2002-03-26 Bridgestone Sports Co., Ltd. Solid golf ball
US7491757B2 (en) 2000-06-15 2009-02-17 China Petroleum & Chemical Corporation Fully cured thermoplastic elastomer, process for its manufacture and applications thereof
US20030045638A1 (en) * 2000-06-15 2003-03-06 Jinliang Qiao Fully cured thermoplastic elastomer, process for its manufacture and applications thereof
US6645089B2 (en) * 2000-08-01 2003-11-11 Sumitomo Rubber Industries, Ltd. Golf ball
US20040220343A1 (en) * 2000-08-11 2004-11-04 Chen John C. Bi-modal ionomers
US20060116478A1 (en) * 2000-08-11 2006-06-01 Chen John C Bi-modal ionomers
US6562906B2 (en) 2000-08-11 2003-05-13 E. I. Du Pont De Nemours And Company Bi-modal ionomers
US6762246B2 (en) 2000-08-11 2004-07-13 E. I. Du Pont De Nemours And Company Bi-modal ionomers
US8193283B2 (en) 2000-08-11 2012-06-05 E. I. Du Pont De Nemours And Company Golf balls with soft, resilient bimodal ionomeric covers
US8410220B2 (en) 2000-08-11 2013-04-02 E I Du Pont De Nemours And Company Golf balls with soft, resilient bimodal ionomeric covers
US7037967B2 (en) 2000-08-11 2006-05-02 E. I. Du Pont De Nemours & Co. Bi-modal ionomers
US20030181595A1 (en) * 2000-08-11 2003-09-25 Chen John C. Bi-modal ionomers
US7148279B2 (en) * 2001-04-13 2006-12-12 Acushnet Company Golf ball compositions comprising dynamically vulcanized blends of highly neutralized polymers and diene rubber
US20040242802A1 (en) * 2001-04-13 2004-12-02 Voorheis Peter R. Golf ball compositions comprising dynamically vulcanized blends of highly neutralized polymers and diene rubber
US6508725B1 (en) * 2001-04-18 2003-01-21 Taylor Made Golf Company, Inc. Golf ball composition and method of manufacture
US9415275B2 (en) 2001-11-28 2016-08-16 Acushnet Company Polybutadiene rubber / ionomer blends for golf balls having multi-layered cores and covers
US8992342B2 (en) 2001-11-28 2015-03-31 Acushnet Company Polybutadiene rubber / ionomer blends for golf balls having dual cores and covers
US20110143864A1 (en) * 2001-11-28 2011-06-16 Sullivan Michael J Polybutadiene rubber / ionomer blends for golf balls having dual cores and covers
US20040132552A1 (en) * 2002-09-27 2004-07-08 Chen John Chu Golf balls with soft, resilient bimodal ionomeric covers
US7144958B2 (en) 2003-05-21 2006-12-05 E. I. Du Pont De Nemours And Company Articles prepared from compositions modified with organic fiber micropulp
US8088026B2 (en) 2006-10-03 2012-01-03 E. I. Du Pont De Nemours And Company Phase transition golf ball and method of use
US20080081710A1 (en) * 2006-10-03 2008-04-03 John Chu Chen Phase transition golf ball and method of use
US20110143863A1 (en) * 2008-01-10 2011-06-16 Sullivan Michael J Golf balls having dual cores made of polybutadiene rubber / ionomer blends
US8784236B2 (en) 2008-01-10 2014-07-22 Acushnet Company Golf balls having dual cores made of polybutadiene rubber / ionomer blends
US9364719B2 (en) 2008-01-10 2016-06-14 Acushnet Company Golf balls having dual cores made of polybutadiene rubber/ionomer blends
US9968831B2 (en) 2008-01-10 2018-05-15 Acushnet Company Golf balls having dual cores made of polybutadiene rubber/ionomer blends
US9102825B2 (en) 2013-09-17 2015-08-11 Nike, Inc. Dynamically crosslinked thermoplastic material process
US9127152B2 (en) 2013-09-17 2015-09-08 Nike, Inc. Dynamically crosslinked thermoplastic material process
US9328224B2 (en) 2013-09-17 2016-05-03 Nike, Inc. Dynamically crosslinked thermoplastic material process
US9481792B2 (en) 2013-09-17 2016-11-01 Nike, Inc. Dynamically crosslinked thermoplastic material process
US9598579B2 (en) 2013-09-17 2017-03-21 Nike, Inc. Dynamically crosslinked thermoplastic material process

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